Manufacture of amino-aryl-acidyl-amino-anthraquinones and their acidyl derivatives.



SATES FIG FRANZ HENLE, 01E HficfisT-ON-THE-MAIN, GERMANY, ASSIGNOR T0 FARBWERKE VORM. MEIS'I'ER LUGIUS & BR llNING, 0F HijGHST-ON-THE-MAIN, GERMAN Y A COR- PORATION OF GERMANY.

No Drawing.

Specification of Letters Patent.

Application filed May 9,

1910. Serial No. 560,344.

To all whom it may concern:

Be it known that I, FRANZ HENLE, Ph. D., l

chemist, a citizenof the Empire of Germany, residing at Hochst-on-the-Mai n, Germany, have invented certain new and useful Improvements in-the Manufacture of Amino- Aryl Acidyl Amino Anthraquinones and Their Acidyl Derivatives, of which the following is a specification.

I have found that hitherto unknown amino-aryl-acidyl-aminoanthraquinones are obtained by reducing the nitro-aryl-acidyl aminoanthraquinones of the general formula anthraquinone) l TI I.C().R.l TO (in which R represents an aromatic residue, such as phenyl, tolyl, anthraquinonyl) such as are, for instance, produced by condensin amincanthraquinones and nitroarylic aci chlorids. The most suitable reducing agents are: hydrosulfite, or zinc dust, or iron and caustic soda lye. The said result of the reaction could not be foreseen, because, first v of all, a saponification of the acidyl derivatives was to be expected.

The bodies obtainable by the present proc ess have the composition (in which R represents any aromatic Example I: 37.2 grams of para-nitroben zoyl-a-aminoanthraquinone are mixed and stirred for some hours at 50-60 C. without access of air, with 500 com. of caustic soda lye of 10% strength and 90 grams of dry sodium hydrosulfite. From the Vl0l6t solution the para-amino-benzoyl-a-aminoanthraquinone is precipitated, wlth an almost theoretical yield, by means of am. This para amino benzoyl-a-aminoanthraquinone when dried is a yellowish-red powder and, on being recrystallized from about 20 parts of nitrobenzene, it forms brownish-red small crystals which melt at over 300 C.

The new product is nearly insoluble in alcohol, ether, acetone, benzene, etc, and yields when treated with hydrochloric acid or sulfuric acid lemon-colored, salts capable of being hydrolyzed. Its yellow solution in concentrated sulfuric acid assumes when heated with trioxymethylene a violet coloration. The paraamino-benzoyl-a-aminoanthraquinone dyes cotton from a violet-red vat brownish-yellow tints.

For obtaining the benzoyl derivative, paraamino benzoyl a aminoanthraquinone is i mixed in a boiling solution of nitrobenzene with a little more than the quantity of benzoyl chlorid calculated for one molecule. The condensation product which forms wit-h evolution of hydrogen chlorid, separates in yellow crystals and is washed with alcohol or ether. Benzoyl para aminobenzoyl a. aminoanthraquinone, which melts at 315 (3..

is difiicultly soluble in the usual organic solvents. It dyes cotton from a violet vat yellow shades. In the same manner yellow condensation products of a high melting point and capable of being recrystallized from nitrobenzene are obtained by substituting for the benzoyl chlorid, described in the above example, the orthoor metaor para nitrobenzoyl chlorid, or the chlorid of anthraquinone-,8-carboxylic acid, the chlorocarbonic acid ester, the succinic acid chlorid, the phthalyl chlorid or the like. Also the anthraquinonyl urea chlorid reacts easily in nitrobenzene solution with para-amino-benzoyl-aminoanthraquinone forming then a yellow condensation product melting at over 300 C. By treatment with phosgen in the cold the correspondin urea chlorid of the constitution C,,H O i Cl is in the/first place obtained and this can be further transformed.

Example II: The brownisl1-yellow paraamino benzoyl 8 aminoanthraquinone of the same manner, may also be recrystallized from nitrobenzene. It is slightly soluble in most of the organic solvents, 1t forms when treated with mineral acid almost colorless Patented Apr. 18, 1911.

can be recrystallized from nitrobenzene and melting point 246 0., which is obtained in benzoyl com ounds, the corresponding derivatives of t e metaor ortho-series areobtamed, viz:--meta-ammo-benzoyl-a-ammoanthraquinone which does not melt within 15 ,of the amino-aryl-aeidyl-aminoanthraqui- 'nones' (Table I.) and of some of the acidylamino aryl acidyl aminoanthraquinones (Table II.), obtainable by the herein described process,

Table I.

gillt'ilgdwhleti Salts otminerel ea w Dyeing cot- Meltln oint. Soiubiiit conc.sulfurle Coloroithevat.

g P acids. acid and up ton. oxymethyiene.

Soluble in nid tro-benzene mflicultl Violet-red..... Brownishp-amlnobenzoylw-aminoanthraquinone..... Over 300.... and pyridin, s olubl yellow. m-amlnobenzoyl-a-aminoanthraqulnone.... Over300..... aimostlnsolemome 1 .....do Yellow. o-aminobenzoyl-a-aminoanthraquinone..... 250 lubie in the Med .....do Redd1sl1- usual orgzmyellow. ic solvents.

. Almost colorp-aminobenzoyi-B-eminoanthraquinone.... do less, other- None Red Yellow. .m-eminobenzoyl-p-eminoenthraquinone.... v21 s.e as .....do ..do Faint-yele. ove. ow. 3.5-dlaminobenzoyl-a-eminoenthraguinone. do Y {Yellow Violet ..do......-.. Yellow 3.o-dlaminobenzoyl-p-eminoauthra iiinone. 202 Colorless None ..do D0. Di-p-emlnobenzoyl-1.5-dieminoantirequi- Infusibie Verydifiioult- Yellow Brownish-vio- ....-.do Reddishnone. ly soluble let. brown.

even in nl- 1 trobenzene. Aminoanthraquinone-cerboxy-a-emlnoen- 230 Prettyreadlly Yellow. For- Violet Blaekish-red.. Brownishthrsquinone. soluble in mation of red.

nitrobensalts occurs zone and in only when ohlorobentreated th zene. high! c ngag rated s. Dlemlnoanthmquinone-earboxy -1.5 dl- Infi1sib1e...-... Insoluble. .....do ..do Almostblaek" Reddishaminoenthraquinone. brown.

w Table II.

From: And: Melting point. Coloroithevat. gki

p-aminobenzoyl-a-aminoanthraquinone Benzoyl ehlo- 315 Verydimeult- Vioiet... Yellow.

, rid. iy soluble. 1

p-aminobenzoyl-a-aminoenthrequlnone Chlorid of an- 280 ..do........ Bleokish-vio- Do. thra uinone let.

car oxylie acid.

p-aminobenzoyl-e-amlnoenthraquinone fl-anthraqui- Over 300..... Ditfloultly Violet Do.

no r l yl urea soluble.

o orid.

m-aminobenzoylu-aminoanthraquinonor ..do.'....... 285 More readily Violet-red"... Do.

' soluble.

p-eminobenzoyl-1i-aminoenthraqulnone ..do Over 800....' ..do Red Do. A

3.6 diaminobenzoyl-o-emlnoenthraqulnone .l p-enthra-qul- At 250" de- .,....do ..do........ Do.

. nonyl urea composed. a

chlorid (2 molecules).

Dl-p-eminobenzoyl-l.s-diamlnoanthraquinone ..do....-. Over 300 Dlflieultly .....do.. Brownishwith decomsoluble. yellow. position.

Amlnoanthraqui.ioneeerboxy-u-amlnoanthrequinone....... Bep oyi chlo- 300. Rp dily solu- 1%m1kdish- Yellow Having, now particulary described my invention, what I claim is:

1. The process of manufacturing aminoaryl-acidyl-aminoanthraquinone, which consists intreating with a reducing agent the condensation products, obtainable in the usual manner by condensing an '-aminoanthraquinone with .a nitroarylic acid chlorid.

2. The process of maunfacturing acidylamino aryl acidyl aminoanthraquinones, which consists in treating with an acidylating agent an aminoarylacidylaminoanthraquinone, obtainable by condensing in the usual manner an aminoanthraquinone Wit-h a nitroarylic acid chlorid and subsequently reducing the condensation product, as hereinbefore described.

3. As new articles of manufacture, aminoaryl-acidyhaminoanthraquinones, obtainable byicondensation of an amino-anthraquinone with a nitroarylic acid chlorid and subsequent reduction; which products are yellow to reddish-brown compounds, insoluble in water, dilute acids and alkalis, soluble only in some organic solvents of high boiling point, such as nitrobenzene, forming, when treated with alkaline hydrosulfite, redto blackcolored vats from which cotton is dyed ellow to brown tints. a

4:. s new articles of manufacture, acidylamino-aryl-acidyl-aminoanthraquinones, obtainable by condensation of an aminoanthraquinone with a nitroarylic acid chlorid, subsequent reduction and acidylation by means of an acid chlorid; which products are yellow to reddish-brown com ounds, insoluble in water, dilute acids an alkalis, soluble only in some organic solvents of high boiling point, such as nitrobenzene, forming, when treated with alkaline hydrosulfite, red to black colored vats, from which cotton is dyed yellow to brown tints.

In testimony whereof, I aiiix my signature in presence of two witnesses.

FRANZ HENLE. Witnesses: v

JEAN GRUND, CARL GRUND. 

